锂离子蓄电池正极材料LiFePO4研究进展

锂离子电池正极材料正在向着高比能量、长寿命、低成本、环境友好的方向发展,而具有橄榄石结构的LiFePO_4正极材料以其结构稳定、成本低、无污染等优点成为21世纪最理想的绿色电源,但自身也存在缺点。综述了锂离子电池正极材料LiFePO_4的研究进展。系统地阐述了LiFePO_4的晶体结构特征及性能、多种合成方法以及掺杂多种导电材料和控制晶体生长制备纳米粉体对材料性能的影响。对该材料的应用前景进行了展望,并提出了下一步可能的研究趋势。     

A simple approach for improving the hybrid MMVB force field: application to the photoisomerization of s-cis butadiene

MMVB is a QM/MM hybrid method, consisting of a molecular mechanics force field coupled to a valence bond Heisenberg Hamiltonian parametrized from ab initio CASSCF calculations on several prototype molecules. The Heisenberg Hamiltonian matrix elements Q(ij) and K(ij), whose expressions are partitioned here into a primary contribution and second-order correction terms, are calculated analytically in MMVB. When the original MMVB force field fails to produce potential energy surfaces accurate enough for dynamics calculations, we show that significant improvements can be made by refitting the second-order correction terms for the particular molecule(s) being studied. This "local" reparametrization is based on values of K(ij) extracted (using effective Hamiltonian techniques) from CASSCF calculations on the same molecule(s). The method is demonstrated for the photoisomerization of s-cis butadiene, and we explain how the correction terms that enabled a successful MMVB dynamics study [Garavelli, M.; Bernardi, F.; Olivucci, M.; Bearpark, M. J.; Klein, S.; Robb, M. A. J Phys Chem A 2001, 105, 11496] were refitted.     

Rigid nanoscopic containers for highly dispersed, stable metal and bimetal nanoparticles with both size and site control

We demonstrate a novel strategy for the preparation of mesoporous silica-supported, highly dispersed, stable metal and bimetal nanoparticles with both size and site control. The supporting mesoporous silica, functionalized by polyaminoamine (PAMAM) dendrimers, is prepared by repeated Michael addition with methyl acrylates (MA) and amidation reaction with ethylenediamine (EDA), by using aminopropyl-functionalized mesoporous silica as the starting material. The encapsulation of metal nanoparticles within the dendrimer-propagated mesoporous silica is achieved by the chemical reduction of metal-salt-impregnated dendrimer-mesoporous silica by using aqueous hydrazine. The site control of the metal or bimetal nanoparticles is accomplished by the localization of inter- or intradendrimeric nanoparticles within the mesoporous silica tunnels. The size of the encapsulated nanoparticles is controlled by their confinement to the nanocavity of the dendrimer and the mesopore. For Cu and Pd, particles locate at the lining of mesoporous tunnels, and have diameters of less than 2.0 nm. For Pd/Pt, particles locate at the middle of mesoporous tunnels and have diameters in the range of 2.0-4.2 nm. The Pd and Pd/Pt nanoparticles are very stable in air, whereas the Cu nanoparticles are stable only in an inert atmosphere.     

Thermodegradation kinetics of a hybrid inorganic-organic epoxy system

Lifetime of the epoxy system formed by diglycidyl ether of bisphenol A, DGEBA/4,4′-diaminediphenylmethane, DDM, modified with the silsesquioxane, glycidylisobutyl-POSS, was calculated from thermogravimetric analysis. The activation energy of the decomposition of this system was evaluated by the integral method developed by Flynn-Wall-Ozawa (E = 88.9 ± 2.1 kJ mol⁻¹) and by Coats and Redfern method (E = 85.2 ± 1.5 kJ mol⁻¹). The kinetic parameters have been used to estimate the lifetime of the system POSS/DGEBA/DDM. The obtained results by two different ways are similar.     

Ring currents as probes of the aromaticity of inorganic monocycles : P5-, As5-, S2N2, S3N3-, S4N3+, S4N42+, S5N5+, S42+ and Se42+

Current-density maps were calculated by the ipsocentric CTOCD-DZ/6-311G** (CTOCD-DZ=continuous transformation of origin of current density-diamagnetic zero) approach for three sets of inorganic monocycles: S(4) (2+), Se(4) (2+), S(2)N(2), P(5) (-) and As(5) (-) with 6 pi electrons; S(3)N(3) (-), S(4)N(3) (+) and S(4)N(4) (2+) with 10 pi electrons; and S(5)N(5) (+) with 14 pi electrons. Ipsocentric orbital analysis was used to partition the currents into contributions from small groups of active electrons and to interpret the contributions in terms of symmetry- and energy-based selection rules. All nine systems were found to support diatropic pi currents, reinforced by sigma circulations in P(5) (-), As(5) (-), S(3)N(3) (-), S(4)N(3) (+), S(4)N(4) (2+) and S(5)N(5) (+), but opposed by them in S(4) (2+), Se(4) (2+) and S(2)N(2). The opposition of pi and sigma effects in the four-membered rings is compatible with height profiles of calculated NICS (nucleus-independent chemical shifts).     

Synthesis of three-layered titanates BaLn<Subscript>2</Subscript>Ti<Subscript>3</Subscript>O<Subscript>10</Subscript> in systems with coprecipitated hydroxocarbonates

The synthesis of three-layered titanates BaLn₂Ti₃O₁₀ (Ln = La, Nd, Sm) in systems with coprecipitated hydroxocarbonates was studied. It was established that they are formed through an intermediate phase with a defective perovskite structure followed by its transformation into the three-layered structure by the ordering of vacancies and rare-earth element and barium atoms and subdivision into three-layered blocks. __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 43, No. 6, pp. 349–353, November–December, 2007.     

Strategies for hydrogen storage in metal--organic frameworks

Increased attention is being focused on metal-organic frameworks as candidates for hydrogen storage materials. This is a result of their many favorable attributes, such as high porosity, reproducible and facile syntheses, amenability to scale-up, and chemical modification for targeting desired properties. A discussion of several strategies aimed at improving hydrogen uptake in these materials is presented. These strategies include the optimization of pore size and adsorption energy by linker modification, impregnation, catenation, and the inclusion of open metal sites and lighter metals.     

Inorganic-Organic Hybrid Polymers from the Polymerisation of Methacrylate-Substituted Oxotantalum Clusters with Methylmethacrylate: A Thermomechanical and Spectroscopic Study

New inorganic-organic hybrid materials were prepared by free-radical polymerization of methyl methacrylate (MMA) with methacrylate-substituted oxotantalum cluster [Ta₄O₄(OEt)₈(OMc)₄] and their properties evaluated. The cluster was prepared by the reaction of the parent alkoxide with methacrylic acid. Samples of the hybrid materials were produced with Ta-cluster to methyl methacrylate in the ratios of 1:50 and 1:100 and were characterized by thermal and spectroscopic techniques. The glass transition temperatures of the hybrid materials are shifted to higher temperatures than pure PMMA as a result of cross-linking of the polymer by the oxotantalum clusters. The increase in T_g is also observed from the dynamic mechanical analysis (DMA). Evidence of crosslinking between the Ta-cluster and PMMA is obtained from infrared spectroscopic study. Surface studies performed by X-ray photoelectron spectroscopy (XPS) provide information about the atomic concentrations of the surface and indicate tantalum bonded to oxygen.     

Cobalt Ion Incorporation into Periodic Mesoporous Organosilica Materials Synthesized by Co-condensation of 1,2-Bistrimethoxysilylethane with 3-Glycidoxypropyltriethoxysilane

Bifunctional periodic mesoporous organosilica materials with and without cobalt ion incorporation were synthesized by co-condensation of 1,2-bistrimethoxysilylethane (BTME) with 3-glycidoxypropyltriethoxysilane (GPTS) in the presence of cetyltrimethylammonium bromide. Nitrogen gas adsorption on samples with varying ratios of BTME:GPTS revealed that increasing the amount of GPTS affects pore size, surface area and pore volume as well as shapes of the isotherms and hysteresis loops. The hysteresis loops of the Type IV isotherms obtained for GPTS-modified ethane silica materials (without cobalt ion) change from Type H3 to Type H4 with increasing GPTS content. There is a tendency for pore sizes to change from mesopore to micropore when the amount of GPTS is increased. Isotherms of cobalt ion incorporated GPTS-modified ethane silica materials change from Type IV to Type I with increasing GPTS content. The surface area, pore volume and pore diameter decrease with increasing loading of GPTS as well as after cobalt ion incorporation. Thermogravimetric analysis and differential thermal analysis show that the surfactant is removed by solvent extraction. Cobalt ion incorporation is confirmed by powder X-ray diffraction and Raman spectroscopy.     

Synthesis, crystal structure, and magnetic properties of the manganate La2Ca2MnO6(O2) related to the hexagonal perovskite-type structure

The compound La₂Ca₂MnO₆(O₂) has been synthesized from La₂Ca₂MnO₇ heated at 1123 K under high pressure (4 GPa) with KClO₃ as oxygen source. The crystal structure has been refined from X-ray powder data in the space group. The unit-cell parameters are a=5.6335(2) Å and c=17.4879(8) Å. Perpendicular to the c-axis, the structure is built up by the periodic stacking of two close packed [LaO₃] layers separated by a layer of composition [Ca₂O₂] containing (O₂)²⁻ peroxide ions. This oxide belongs to the family of compounds formulated as [A′₂O_2−δ][A_nB_n−1O_3n] for n=2 and δ=0. It is the first member of the series where the thickness of the perovskite slab corresponds to one [BO₆] (B=Mn) octahedron. The structural relationships with La₂Ca₂MnO₇ are discussed and the magnetic properties show that in both phases manganese is tetravalent.